US5905118A - Miscible polymers - Google Patents

Miscible polymers Download PDF

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Publication number
US5905118A
US5905118A US09/051,741 US5174198A US5905118A US 5905118 A US5905118 A US 5905118A US 5174198 A US5174198 A US 5174198A US 5905118 A US5905118 A US 5905118A
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polymer
styrene
polymers
weight percent
monomer
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US09/051,741
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English (en)
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Allen Robert Padwa
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Bayer Antwerpen NV
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Bayer Antwerpen NV
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Priority to PCT/US1995/014743 priority Critical patent/WO1997016487A1/en
Application filed by Bayer Antwerpen NV filed Critical Bayer Antwerpen NV
Priority to ES95941383T priority patent/ES2145939T3/es
Priority to US09/051,741 priority patent/US5905118A/en
Priority to CA002235934A priority patent/CA2235934A1/en
Priority to DE69516912T priority patent/DE69516912T2/de
Priority to EP95941383A priority patent/EP0858482B1/de
Assigned to BAYER ANTWERPEN SA/NV reassignment BAYER ANTWERPEN SA/NV ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MONSANTO COMPANY
Assigned to BAYER ANTWERPEN N.V. reassignment BAYER ANTWERPEN N.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MONSANTO COMPANY
Assigned to BAYER ANTWERPEN S.A./N.V. reassignment BAYER ANTWERPEN S.A./N.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PADWA, ALLEN ROBERT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/02—Homopolymers or copolymers of monomers containing phosphorus

Definitions

  • the present invention relates to terpolymers of a vinyl aromatic monomer such as styrene, ⁇ -methylstyrene, chlorostyrene and the like; an unsaturated nitrile monomer such as acrylonitrile, methacrylonitrile and the like and a dialkylvinyl aromatic phosphonate and to miscible blends thereof with certain polymers such as poly(styrene acrylonitrile) polymers (SAN) and polymers and copolymers of methylmethacrylate.
  • SAN poly(styrene acrylonitrile) polymers
  • S styrene
  • AN acrylonitrile
  • DMSP dimethylstyrene phosphonate
  • PMMA polymethylmethacrylate
  • Polymers containing phosphonic acid groups are known in the art. Examples include styrene/1-phenylvinylphosphonic acid copolymers (Plast. Massy, No. 8 (1966)24), crosslinked vinyl phosphonate copolymers (U.S. Pat. No. 3,726,839), and styrenic polymers that contain pendent phosphonate ester groups J. Polym. Sci. Polym. Chem. Ed. A 28 (1990) 227;27 (1989) 3985!.
  • Phosphorus compounds have been used to impart flame retardance to a number of polymer systems (see Huggard, M. T. 1993, New Intumescent Phosphorus-Based Fire Retardants, Plastics Engineering, 49, 28). In mixtures of polymers such as ABS with main-chain aromatic polymer such as polycarbonate, phosphorous based compounds can impart flame retardance (see Witgosky, V. Flame Retardants, Plast. Eng. 49,10,21).
  • organophosphorus compounds while minimizing some of the environmental concerns of halogens, can still result in performance changes due to plasticization and migration. Incorporation of bound phosphorous functional groups into the polymer structure opens up the possibility of new performance regimes.
  • novel styrenic compositions which contain phosphorous and which are miscible with polymers such as styrene acrylonitrile polymers (SAN) and polymers and copolymers of methylmethacrylate.
  • the novel styrenic compositions comprise at least one vinyl aromatic monomer, at least one unsaturated nitrile monomer and a dialkylvinylaromatic phosphonate.
  • the preferred vinylaromatic monomers are styrene, alphamethyl styrene, vinyl toluene, halostyrenes, e.g. bromo- or chloro-styrene, paramethyl styrene and the like.
  • the preferred unsaturated nitrile monomers are acrylonitrile and methacrylonitrile with acrylonitrile being more preferred.
  • the foregoing monomers may also be used to prepare variations of the SAN used in the miscible blends with the phosphorous containing polymer.
  • the preferred alkyls used in the dialkyl phosphonates are C 1 to C 10 alkyls with methyl, ethyl and propyl being preferred.
  • the resulting miscible compositions of the S/AN/DMSP and the SAN components may further contain rubbery polymers such as methylacrylate-butadiene-styrene polymers (MBS), acrylonitrile-butadiene-styrene polymers (ABS), acrylonitrile-styrene-acrylate rubber polymers (ASA), acrylonitrile-styrene-ethylene propylene diene monomer polymers (EPDM-g-SAN) and the like.
  • the phosphorous component contributes to flame retardance while the rubber components impart toughness.
  • the sole drawing is a diagram showing the glass transition temperature (T g ) of 50/50 blends of SAN with a S/AN/DMSP polymer as a function of the weight percent of AN in the SAN.
  • the S/AN/DMSP polymers of the present invention contain from 40 to 84 weight percent of styrene (S), from 15 to 35 weight percent of acrylonitrile (AN) and from 1 to 25 weight percent of dimethylstyrene phosphonate.
  • S styrene
  • AN acrylonitrile
  • DMSP dimethylstyrene phosphonate
  • the amount of styrene is in the range of from 50 to 70 weight percent
  • the amount of acrylonitrile is in the range of from 20 to 30 weight percents
  • the DMSP is in the range of from 10 to 20 weight percent. All weight percents being based on the total weight of the S/AN/DMSP polymer.
  • the S/AN/DMSP polymer is prepared by conventional polymerization methods such as emulsion, suspension, solution, bulk or mass techniques.
  • One method of such a preparation is shown in Example 1 below.
  • the DMSP was copolymerized with styrene (S) and/or acrylonitrile (AN).
  • S and AN used were commercial grade monomers which were purified to remove inhibitor using catechol and quinone removal aluminas, respectively, which aluminas were obtained from Scientific Polymer Products, Ontario, N.Y.
  • the polymerization initiator used was azobisisobutyronitrile (AIBN), reagent grade from Aldrich Chemical.
  • Monomer and initiator mixtures were sealed under nitrogen in 5 mm glass tubes after freezing the mixtures with dry ice.
  • the initiator concentration was 0.066 wt % except where noted. All polymerizations were carried out without solvent.
  • the contents of the tubes were polymerized at 70° C. for the required time.
  • the subsequent solution of polymer in monomers (about 5 gm) were poured into a tared 50 ml glass centrifuge tube and weighed.
  • the polymer was precipitated with 30 ml of methanol and spun at 5000 rpm. After decanting and drying, in vacuo, at 80° C. overnight, the dry polymer was weighed and used for subsequent analysis. For composition and molecular weight determination, samples of near 1% conversion were chosen.
  • composition of the polymer was determined by automated Carlo-Erba C--H--N analysis. Phosphorus content was determined by Galbraith Labs (Knoxville, Tenn.). Molecular weight was estimated by automated size exclusion chromatography in tetrahydrofuran using four columns containing a mixed pore-size bed of 5 ⁇ m beads (Polymer Laboratories, Amherst, Mass.) The flow rate was 1 ml min -1 at 35° C. with a refractive index detector. Molecular weights were estimated using the universal calibration method and are reported in polystyrene equivalents.
  • compositions of the polymers prepared in Examples 1 to 11 are summarized in Table I below.
  • Examples 8 to 11 show the S/AN/DMSP terpolymers of the present invention.
  • the amount of DMSP in the terpolymer varies from 4.9 to 19.7% by weight based on the total weight of the terpolymer.
  • the amount of AN in the terpolymer varies from 18.1 to 20.3.
  • the amount of styrene is by difference.
  • the T g of the terpolymers in Examples 8 to 11 generally increases with increasing amounts of DMSP.
  • Polymer blends were prepared by casting a 1:1 (weight/weight) mixture of the S/AN/DMSP and SAN or PMMA polymer as a 5 wt % solution in 2-butanone into warmed (about 75° C.) Petri dishes. After evaporation of the solvent, the film was removed from the glass and dried, in vacuo, at 120° C. overnight. The resulting film was scanned at 20° C./min. in a Perkin-Elmer DSC-2 scanning calorimeter under nitrogen from 30 to 200° C. To minimize the effect of thermal stresses on the T g measurement, the reported data is the result of the scan obtained after quenching from 200° C.
  • the S/AN/DMSP terpolymer of Example 10 containing 19.9 wt % of acrylonitrile and 14.2 wt % of DMSP was solution blended with a series of SAN copolymers of varying AN contents and similar molecular weights (Mw/Mn about 100,000/50,000), solvent cast, dried, annealed and tested.
  • the S/AN/DMSP terpolymer of Example 12 was blended with V-811, a polymethylmethacrylate (PMMA) obtained from Rohm and Haas Company (Philadelphia, Pa.), solvent cast, dried, annealed and tested.
  • PMMA polymethylmethacrylate
  • miscible blends may be used as is or added to conventional ABS, MBS, ASA, ASEPDM polymers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dental Preparations (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US09/051,741 1995-11-03 1995-11-03 Miscible polymers Expired - Fee Related US5905118A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
ES95941383T ES2145939T3 (es) 1995-11-03 1995-11-03 Polimeros miscibles.
US09/051,741 US5905118A (en) 1995-11-03 1995-11-03 Miscible polymers
CA002235934A CA2235934A1 (en) 1995-11-03 1995-11-03 Miscible polymers
DE69516912T DE69516912T2 (de) 1995-11-03 1995-11-03 Mischbare polymere
PCT/US1995/014743 WO1997016487A1 (en) 1995-11-03 1995-11-03 Miscible polymers
EP95941383A EP0858482B1 (de) 1995-11-03 1995-11-03 Mischbare polymere

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/051,741 US5905118A (en) 1995-11-03 1995-11-03 Miscible polymers
CA002235934A CA2235934A1 (en) 1995-11-03 1995-11-03 Miscible polymers
PCT/US1995/014743 WO1997016487A1 (en) 1995-11-03 1995-11-03 Miscible polymers

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US5905118A true US5905118A (en) 1999-05-18

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CA (1) CA2235934A1 (de)
DE (1) DE69516912T2 (de)
ES (1) ES2145939T3 (de)
WO (1) WO1997016487A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050075455A1 (en) * 2003-10-01 2005-04-07 Chang Moh-Ching O. Thermoplastic molding composition having high clarity

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104945761A (zh) * 2015-07-28 2015-09-30 太仓市晨洲塑业有限公司 一种改性聚苯乙烯塑料

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3726839A (en) * 1970-10-28 1973-04-10 Stauffer Chemical Co Fire retardant crosslinked copolymers of a bis(hydrocarbyl)phosphonate with a polyfunctional ethylenically unsaturated monomer
US5237028A (en) * 1991-12-12 1993-08-17 Arco Chemical Technology, L.P. Organic liquid absorbent compositions based on phosphonic acid-containing polymers and di- or polyamines
US5274050A (en) * 1991-12-12 1993-12-28 Arco Chemical Technology, L.P. Organic liquid absorbent compositions based on phosphonic acid-containing polymers and di- or polyamines

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH064691B2 (ja) * 1986-05-09 1994-01-19 大阪府 難燃性樹脂の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3726839A (en) * 1970-10-28 1973-04-10 Stauffer Chemical Co Fire retardant crosslinked copolymers of a bis(hydrocarbyl)phosphonate with a polyfunctional ethylenically unsaturated monomer
US5237028A (en) * 1991-12-12 1993-08-17 Arco Chemical Technology, L.P. Organic liquid absorbent compositions based on phosphonic acid-containing polymers and di- or polyamines
US5274050A (en) * 1991-12-12 1993-12-28 Arco Chemical Technology, L.P. Organic liquid absorbent compositions based on phosphonic acid-containing polymers and di- or polyamines
US5340883A (en) * 1991-12-12 1994-08-23 Arco Chemical Technology, L.P. Organic liquid absorbent compositions based on phosphonic acid-containing polymers and di- or polyamines

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
Chem. Abstracts, vol. 108, No. 22, May 30, 1998, Abstract No. 187541. *
Chem. Abstracts., vol. 72, No. 4, Jan. 26, 1970, Abstract No. 13116. *
Huggard M. T. 1993, new Intumenscent Phosphorus Based Fire Retardants, Plastics Engineering 49, Nov. 1993, 29. *
Huggard M. T. 1993, new Intumenscent Phosphorus-Based Fire Retardants, Plastics Engineering 49, Nov. 1993, 29.
J. Polym. Sci. Polym. Chem. Ed. A 28 (1990) 227; 27 (1989) 3985. *
Journal of Polymer Science, vol. 18, No. 7, Jul. 1974, I. Cabasso et al, pp. 1969 1986. *
Journal of Polymer Science, vol. 18, No. 7, Jul. 1974, I. Cabasso et al, pp. 1969-1986.
Polymer, vol. 35, No. 16, 1994, Lancaster, UK, pp. 3470 3473, M. Banks et al. *
Polymer, vol. 35, No. 16, 1994, Lancaster, UK, pp. 3470-3473, M. Banks et al.
Wigotsky, V., Flame Retardants, Plast. Eng 49, 10, Oct. 1993, 20. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050075455A1 (en) * 2003-10-01 2005-04-07 Chang Moh-Ching O. Thermoplastic molding composition having high clarity
US7265180B2 (en) * 2003-10-01 2007-09-04 Lanxess Corporation Thermoplastic molding composition having high clarity

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DE69516912D1 (de) 2000-06-15
DE69516912T2 (de) 2000-10-05
ES2145939T3 (es) 2000-07-16
CA2235934A1 (en) 1997-05-09
EP0858482A1 (de) 1998-08-19
WO1997016487A1 (en) 1997-05-09
EP0858482B1 (de) 2000-05-10

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